Physico-Chemical and Chromatic Characterization of Malvidin 3-Glucoside-vinylcatechol and Malvidin 3-Glucoside-vinylguaiacol Wine Pigments

[EN] The physicochemical and chromatic features of malvidin 3-glucoside-vinylcatechol (PA1) and malvidin 3-glucoside-vinylguaiacol (PA2) adducts were investigated. Important differences between both pigments were observed. In the investigated pH range (2.0−4.5), our results suggest that PA1 could be considered as a noncovalent dimer of two pyranoflavylium ions (AH)2 which undergo a hydration reaction in two successive steps, with no proton transfer. In contrast, only proton transfer equilibrium between the pyranoflavylium ion and the quinonoid bases was observed for PA2. The hydration and acidity thermodynamic constants of both pyranoanathocyanins were determined by UV−vis spectroscopy. Pigment PA1 was shown to be less sensitive to bisulfite addition than to water addition, and PA2 seems to be largely insensitive to both water and bisulfite additions. The binding constants for the interaction between the pigments and (+)-catechin in aqueous solution and the changes in the CIELAB parameters that it provoked were also determined. The huge increase in the absorption of the pyranoflavylium ion of PA2 when it binds catechin has no equivalent for anthocyanins and nicely outlines the potential of pyranoanthocyanins in the expression of natural colors

Extractability of Low Molecular Mass Flavanols and Flavonols from Red Grape Skins. Relationship to Cell Wall Composition at Different Ripeness Stages

[EN] Flavonol and flavan-3-ol extractabilities from red grape skins were evaluated in Tempranillo grapes harvested at different ripeness stages and with different soluble solid contents within each stage. Flavan-3-ol extractability is related to ripeness stage and also to cell wall composition, mainly to arabinogalactans (AG), mannans, rhamnogalacturonans-I (RG-I), homogalacturonans (HG), xyloglucans (XG), and total polysaccharides content, which are negatively correlated to flavan-3-ol extractability, whereas soluble solid content did not exert any influence on their extraction. Moreover, procyanidin extraction is more strongly related to cell wall composition than prodelphinidin extraction. Flavonol extractability was not influenced by insoluble material contents; although some cell wall components presented a relationship with flavonol extractability, the presence of AG and mannans would decrease total flavonol extractability, whereas protein is positively related to total and major flavonol compounds (i.e., quercetin and myricetin derivatives). The different behaviors observed between those two groups of polyphenol compounds could be due to different tissue and cellular location

Influence of the physiological stage and the content of soluble solids on the anthocyanin extractability of Vitis vinifera L. cv. Tempranillo grapes

[EN] The influence and the extent of the anthocyanin extractability from grape skins at different physiological stages and different soluble solids contents within each stage were investigated. For this purpose three different physiological stages (pre-harvest, harvest and over-ripening) and three soluble solids contents (22, 24 and 26 °Brix) within each stage were taken into account using Vitis vinifera L. cv. Tempranillo. This study revealed the influence of physiological stages and soluble solids contents on the amounts of anthocyanins. The most important factor was the physiological stage although the soluble solid contents effect was also relevant, especially for anthocyanins monoglucosides. The highest contents in anthocyanins were found at pre-harvest, following by harvest and finally at over-ripening. Within each physiological stage, the relative abundance of acylated derivatives was influenced by the soluble solids contents. The percentages of acylated anthocyanins tend to decrease as the soluble solids contents. Differences in the anthocyanin extractabilities were highly influenced by the physiological stages and in a lesser extent by the soluble solids contents. The lowest extraction percentages were obtained in pre-harvest samples whatever soluble solids contents. Over-ripening samples present the lowest contents of anthocyanins but these compounds are easily released from tissues to the hydroalcoholic solution providing the highest extraction percentages. Generally, non-acylated anthocyanins were better extracted than the acylated anthocyanins

Effect of the addition of flavan-3-ols on the HPLC-DAD salivary-protein profile

[EN] The interaction between monomeric flavan-3-ols and salivary proteins has been studied using HPLC-DAD. A chromatographic method has been described and seven protein fractions were collected. The peptides and proteins present in each fraction have been identified using nLC-MS-MS analysis. The interaction between saliva and catechin, epicatechin and gallocatechin has been studied. These compounds interact in a discriminated way with salivary proteins: catechin causes a decrease of some fractions, epicatechin causes the decrease or increase of fractions while gallocatechin seems to cause an increase of two fractions. This variable behavior is explained, for the decrease in the chromatographic area, by the precipitation of salivary proteins and, for the increase of the area, by the formation of soluble complexes and/or for the formation of new peaks

Impact of postharvest dehydration process of winegrapes on mechanical and acoustic properties of the seeds and their relationship with flavanol extraction during simulated maceration

[EN] This study represents the first time that the extraction of phenolic compounds from the seeds is assessed from instrumental texture properties for dehydrated grapes. Nebbiolo winegrapes were postharvest dehydrated at 20 °C and 41% relative humidity. During the dehydration process, sampling was performed at 15%, 30%, 45% and 60% weight loss. The extractable fraction and extractability of phenolic compounds from the seeds were determined after simulated maceration. The evolution of mechanical and acoustic attributes of intact seeds was also determined during grape dehydration to evaluate how these changes affected the extraction of phenolic compounds. The extractable content and extractability of monomeric flavanols and proanthocyanidins, as well as the galloylation percentage of flavanols, might be predicted easily and quickly from the mechanical and acoustic properties of intact seeds. This would help in decision-making on the optimal dehydration level of winegrapes and the best management of winemaking of dehydrated grapes

Characterization of Sensory Properties of Flavanols--A Molecular Dynamic Approach

[EN] In this work, sensations elicited by catechin and procyanidins in comparison with those elicited by gallocatechin and prodelphinidins were evaluated by means of a sensory panel. To obtain further insights into the mechanisms of action, molecular dynamics (MD) simulations and saturation transfer difference nuclear magnetic resonance (STD NMR) experiments have been performed. Results showed clear differences between the 2 types of flavanols. Dihydroxylated B-ring flavanols were more astringent, bitter, dry, rough, unripe, and persistent than trihydroxylated B-ring ones. Besides, these last compounds were smoother, more velvety, and viscous. MD simulations and STD NMR experiments support results obtained from tasting panel. MD results suggested that catechin binds to a human salivary proline-rich peptide IB714 faster than gallocatechin and this interaction is maintained longer. IB714 can interact with 2 catechin molecules concurrently while only interacts with 1 gallocatechin molecule. Accordingly, STD NMR experiments showed a greater affinity of catechin than gallocatechin for the peptide (KD = 2.7 and 25.7, respectively). Results indicate that the number of hydroxyl substituents present in B-ring of the flavanic nucleus is decisive for the interaction with salivary proteins and the development of astringency perception

Relationship between skin cell wall composition and anthocyanin extractability of Vitis vinifera L. cv. Tempranillo at different grape ripeness degree

[EN] The relationship between cell wall composition and extractability of anthocyanins from red grape skins was assessed in Tempranillo grape samples harvested at three stages of ripening (pre-harvest, harvest and over-ripening) and three different contents of soluble solids (22, 24 and 26 !Brix) within each stage. Cell wall material was isolated and analysed in order to determine cellulose, lignin, non-cellulosic poly- saccharides, protein, total polyphenols index and the degree of esterification of pectins. Results showed the influence of ripeness degree and contents of soluble solids on cell wall composition. Furthermore, principal components analysis was applied to the obtained data set in order to establish relationships between cell wall composition and extractability of anthocyanins. Total insoluble material exhibits the biggest opposition to anthocyanin extraction, while the highest amounts of cellulose, rhamnogalacturonans-II and polyphenols were positively correlated with anthocyanin extraction. Moreover, multiple linear regression was performed to assess the influence of the cell wall composition on the extraction of anthocyanin compounds. A model connecting cell wall composition and anthocyanin extractabilities was built, explaining 96.2% of the observed variability

Optimisation of an oak chips-grape mix maceration process. Influence of chip dose and maceration time

[EN] Oak chips-related phenolics are able to modify the composition of red wine and modulate the colour stability. In this study, the effect of two maceration techniques, traditional and oak chips-grape mix process, on the phenolic composition and colour of Syrah red wines from warm climate was studied. Two doses of oak chips (3 and 6 g/L) at two maceration times (5 and 10 days) during fermentation was considered. Changes on phenolic composition (HPLC–DAD–MS), copigmentation/polymerisation (spectrophotometry), and colour (Tristimulus and Differential Colorimetry) were assessed by multivariate statistical techniques. The addition of oak chips at shorter maceration times enhanced phenolic extraction, colour and its stabilisation in comparison to the traditional maceration. On contrast, increasing chip dose in extended maceration time resulted in wines with lighter and less stable colour. Results open the possibility of optimise alternative technological applications to traditional grape maceration for avoiding the common loss of colour of wines from warm climate

Trying to set up the flavanolic phases during grape seed ripening: A spectral and chemical approach

[EN] Grape seeds were collected in ten different dates and classified in seven groups according to their individual hyperspectral imaging characteristics. Proanthocyanidin composition was studied using HPLC-MS for oligomers and acid catalyzed cleavage for polymers characterization. The combination of both analysis provided a complete description of the flavanols. Chemometric analysis was performed to summarize the analytical results. None of the considered variables presented statistical differences among all groups. From one to five groups were found for each variable, while three was the most frequent value, consequently three putative stages might be considered the real number of different analytical stages since it is the number of statistically significant groups for the majority of the compounds. This classification could be considered as the first step to optimize the use of seeds in winemaking to minimize the gap between sugar and phenolic maturities, consequence of the global climate change, mainly observed in warm climate